Premium
Kinetics, mechanism, and stereochemistry of Diels‐Alder reactions of CN‐substituted ethenes with cyclohexa‐1, 3‐diene in the gas phase
Author(s) -
Van Mele B.,
Huybrechts G.
Publication year - 1987
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.550190407
Subject(s) - chemistry , diene , kinetics , gas phase , reaction mechanism , stereochemistry , medicinal chemistry , organic chemistry , catalysis , physics , natural rubber , quantum mechanics
The kinetics of the Diels‐Alder additions of CH 2 = CHCN, CH 2 = C(CH 3 ) CN, and cis ‐ and trans ‐CH 3 CH = CHCN to cyclohexa‐1, 3‐diene have been studied in the gas phase. The stereochemistry of these reactions is discussed. In terms of a biradical mechanism, a minimum value of 4.1 ± 0.8 kcal mol −1 for the stabilizing effect of a CN group vis‐à‐vis a methyl group is shown to fit the experimental activation energies.